Process for the alkoxylation of organic compounds in the presence of novel framework materials

ABSTRACT

The present invention relates to a process for the alkoxylation of organic compounds comprising the reaction of at least one organic compound with at least onealkoxylating agent in the presence of a catalyst system, wherein a polyetheralcohol is obtained. The catalyst system comprises a metallo organic framework mate-rial comprising pores and at least one metal ion and at least one at least bidentate organic compound, which is coordinately bounded to said metal ion. Furthermore it relates to polyurethanes or polyurethane foams, which are obtainable by using a prepared polyether alcohol as a starting material.

[0001] The present invention relates to a process for the alkoxylationof organic compounds in the presence of catalyst systems comprising ametallo-organic framework material comprising pores and a metal ion andan at least bidentate organic compound, said bidentate organic compoundbeing coordinately bound to the metal ion. The invention furtherencompasses an integrated process for preparing polyurethanes fromisocyanate and polyether alcohol or modified polyether alcohols, whichhave been obtained by using the alkoxylation process according to theinvention. Still further, the present invention is directed topolyurethanes being obtainable by the process according to theinvention, as well as shaped bodies comprising the polyurethanes asprepared according to the invention.

[0002] The polyurethanes prepared according to the invention areparticularly useful for the preparation of polyurethane foams,polyurethane cast skins and elastomers.

[0003] The characteristics of polyurethanes, such as mechanicalproperties and smell, are particularly strongly dependent upon theisocyanate and polyether alcohols, which are respectively used for theirpreparation, and optionally upon the used driving agents. Particularlythe structure of the polyether alcohol has a strong influence on thecharacteristics of the obtained polyurethane. The properties of thepolyether alcohols are in turn strongly influenced by their method ofpreparation and particularly by the characteristics and the process forpreparation of the starting materials. A detailed discussion of thephenomena may be found in WO 01/7186 and DE 10143195.3 of the presentapplicant. As further prior art for preparing polyether alcohol, WO01/16209 and WO 00/78837 are to be mentioned.

[0004] The reduction of the impurities within the preparation ofpolyether alcohols and/or polyurethanes is of high interest for variousapplications. The automotive and furniture industry request inincreasing amounts polyurethanes, which possibly are free of emissionsand smelling substances. According to the guideline of Daimler Chryslerdenoted PB VWL 709 of Jan. 11, 2001 it is required that parts to be usedinside of cars exhibit a maximum of 100 ppm for the emission of volatilesubstances and 250 ppm for condensable substances, respectively.

[0005] Impurities, which are present in polyurethanes also negativelyinfluence the mechanical properties thereof. The impurities and sidereactions in many cases lead to mono-functional products. Thefunctionality of the polyetheroles and the mechanical properties of thepolyurethanes, such as elongation, tear strength and hardness generallydeteriorate.

[0006] Polyether alcohols may be prepared e.g. by way of base or acidcatalyzed polyaddition of alkaline oxides to polyfunctional organiccompounds (starters). Suitable starters are e.g. water, alcohols, acidsor amines or mixtures of two or more thereof. These preparation methodsare particularly disadvantageous in that several elaborate purifyingsteps are necessary in order to separate the catalyst residue from thereaction product. Furthermore, with increasing chain length of polyetherpolyoles prepared, the content of mono-functional products andsubstances with intensive smell, which are not desired withinpolyurethane production, increases.

[0007] The reduction of the functionality is particularlydisadvantageous for elastomers, since the used polyether alcohols shouldgenerally be bi-functional. Due to the mono-functional impurities withinthe polyether alcohol, the functionality decreases below 2, resulting ina significant deterioration of the mechanical characteristics of thepolyurethanes, particularly tear strength and elongation.

[0008] The side products generated by side reactions within the base oracid catalyzed reaction are furthermore partly contained in thepolyurethane as smelling impurities. Particularly to be mentioned arealdehydes, e.g. propionic aldehyde, cycloacetates, allylic alcohol andtheir reaction products. The automotive and furniture industry requestin increasing amounts polyetheroles and polyurethanes having reduced orno smell.

[0009] An object of the invention is therefore to provide a process forthe preparation of polyether alcohols and polyurethanes, respectively,which yields polyether alcohols and polyurethanes, respectively, havinga low amount of impurities, particularly low molecular weight substanceshaving intensive smell, which process does not comprise elaboratepurifying steps of starting materials and/or intermediate products.

[0010] This object is solved by a process for the alkoxylation oforganic compounds comprising the reaction of at least one organiccompound, which is capable of being alkoxylated, with at least onealkoxylating agent in the presence of a catalyst system, wherein apolyether alcohol is obtained. This process is characterized in that thecatalyst system comprises a metallo-organic framework materialcomprising pores and at least one metal ion and at least one at leastbidentate organic compound, which is coordinately bound to said metalion. Furthermore it is solved by an integrated process for thepreparation of a polyurethane comprising at least the following steps:

[0011] (2) reacting at least one organic compound, which is capable ofbeing alkoxylated, with at least one alkoxylating agent via a process asdescribed above, wherein a polyether alcohol is obtained;

[0012] (3) reacting the polyether alcohol of step (2) with at least oneisocyanate.

[0013] As the alkoxylating agent in step (2) preferably mono- ormultifunctional expoxide having two to 30 carbon atoms or mono- ormultifunctional polyester polyoles having a molar mass of above 600g/mol or a mixture of two or more thereof are used. Particularly,substituted or unsubstituted alkylene oxides having two to 24 C-atoms,e.g. alkylene oxides having halogen, hydroxy, non-cyclic ether orammonium substituents are used.

[0014] As suitable compounds, the following are exemplarily to bementioned: ethylene oxide, 1,2-epoxypropane, 1,2-methyl-2-methylpropane,1,2-epoxybutane, 2,3-epoxybutane, 1,2-methyl-3-methylbutane,1,2-epoxypentane, 1,2-methyl-3-methylpentane, 1,2-epoxyhexane,1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane,1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxycyclopentane,1,2-epoxycyclohexane, (2,3-epoxypropyl)benzene, vinyloxirane,3-phenoxy-1,2-epoxypropane, 2,3-epoxymethyl ether, 2,3-epoxylethylether, 2,3-epoxyl isopropyl ether, 2,3-epoxyl-1-propanol,(3,4-epoxybutyl)stearate, 4,5-epoxypentylacetate, 2,3-epoxy propanemethacrylate, 2,3-epoxy propane acrylat, glycidylbutyrate,methylglycidate, ethyl-2,3-epoxybutanoate,4-(trimethylsilyl)butane-1,2-epoxide,4-(triethylsilyl)butane-1,2-epoxide, 3-(perfluoromethyl)propane oxide,3-(perfluoroethyl)propane oxide, 3-(perfluorobutyl)propane oxide,4-(2,3-epoxypropyl)morpholine, 1-(oxirane-2-ylmethyl)pyrrolidin-2-one,and mixtures of two or more thereof.

[0015] Particularly to be mentioned are: aliphatic 1,2-alkylene oxidehaving 2 to 4 C-atoms, such as ethylene oxide, 1,2-butylene oxide,2,3-butylene oxide or isobutylene oxide, aliphatic 1,2-alkylene oxideshaving 5 to 24 C-atoms, cycloaliphatic alkylene oxide, such ascyclopentane oxide, cyclohexane oxide orcyclododecatriane-(1,5,9)-monoxide, araliphatic alkylene oxide, e.g.styrene oxide.

[0016] Particularly preferred are within the present invention ethyleneoxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, styrene oxide,vinyloxirane and any mixtures of two or more thereof within each other,particularly ethylene oxide, propylene oxide and mixtures of ethyleneoxide, 1,2-epoxypropane.

[0017] As polyether alcohols, within the present invention, particularlypolyester polyoles and modified polyetheroles are used, which areobtainable by using ethylene oxide or propylene oxide, which may beprepared according to step (1), preferably according to an embodimentoutlined hereinunder. Subsequently, step (1) of the present invention isexemplarily described in detail by use of propylene oxide as an example:

[0018] Generally, propylene oxide may be obtained by reacting propylenewith oxygen; hydrogen and oxygen; hydrogen peroxide; organichydroperoxides; or halohydrines, preferably by reacting propylene withhydrogen peroxide, more preferred by reacting propylene with hydrogenperoxide in the presence of a catalyst comprising a zeolithic material,particularly by reacting propylene with hydrogen peroxide in thepresence of a catalyst comprising a titanium-containing zeolithicmaterial having CS-1-structure.

[0019] As a particularly suitable hydroperoxide for the epoxidationaccording to step (1), hydrogen peroxide is to be mentioned. This can beeither prepared outside the reaction according to (1) or by startingfrom hydrogen and oxygen in situ within the reaction according to (1),respectively.

[0020] Thus, the present invention also relates in a preferredembodiment to a process for the alkoxylation of organic compounds and anintegrated process for preparing a polyurethane, respectively, whereinthe hydroperoxide as used in step (1) is hydrogen peroxide.

[0021] The epoxidation according to step (1) is in principle known frome.g. DE 100 55 652.3 and further patent applications of the presentapplicant, such as DE 100 32 885.7, DE 100 32 884.9, DE 100 15 246.5, DE199 36 547.4, DE 199 26 725.1, DE 198 47 629.9, DE 198 35 907.1, DE 19723 950.1, which are fully encompassed within the content of the presentapplication with respect to their respective content. By the epoxidationaccording to step (1), propylene oxide is obtained in high purity.Particularly, the propylene oxide as such obtained exhibits a content ofC₆-compunds of <1 ppm.

[0022] Within the present invention, as C6-compounds e.g. the followingcompounds are underdstood: 2-methylpentane, 4-methylpentene-1, n-hexane,hexenes, such as 1-hexene, and components having 6 C-atoms and inaddition thereto one or more functional groups selected among the classof aldehydes, carboxylic acids, alcohols, ketones and ethers. Furtherundesired impurities are propane derivatives, particularly chlorinatedpropane derivatives, acetaldehyde, propione aldehyde, acetone,dioxolanes, allylic alcohol, pentane, methylpentane, furane, hexane,hexene, methoxypropane and methanol.

[0023] The propylene oxide obtained according to step (1) may furthercomprise as further side components, up to 100 ppm, particularly up to40 ppm, methanol and up to 10 ppm, preferably up to 4 ppm, acetaldehyde.

[0024] Compared to other known methods for preparing propylene oxide,which are not excluded from the present application, and which are e.g.described in Weissermel, Arpe “Industrielle Organische Chemie”,publisher VCH, Weinheim, 4^(th) Ed., pages 288 to 318, the preferredembodiments of step (1) according to the invention yields propyleneoxide having only minor impurities of C₆-components and contain nochloro-organic impurities.

[0025] A summary of the above-referenced prior art and the procedurewhen preparing polyether alcohols starting from propylene oxide is givenin DE 10143195.3.

[0026] With regard to the preparation of ethylene oxide, which may alsoserve as an alkoxylating agent and which may also be prepared prior toconducting the process for the alkoxylation of an organic compound beingcapable of being alkoxylated, is e.g. broadly disclosed in U. Onken,Anton Behr, “Chemische Prozesskunde”, Vol. 3, Thieme, 1996, pages 303 to305 and Weissermel, Arpe “Industrial Organic Chemistry”, 5^(th) Ed.,Wiley, 1998, pages 159 to 181.

[0027] Within the reaction yielding the polyether alcohols, thealkoxylating agent obtained according to step (1), particularlypropylene oxide, may be directly used in the reaction according to step(2). It is, however, also possible within the present invention that thealkoxylating agent, particularly propylene oxide, yielded according tostep (1) is beforehand treated, e.g. purified. As the purificationmethod, mention can be made of a fine distillation. Suitable processesare e.g. disclosed in EP-B 0 557 116.

[0028] The alkoxylating agent as obtained according to step (1),particularly propylene oxide, may be used within the present inventionalone or together with at least one further alkoxylating agent,particularly together with at least one further alkylene oxide.

[0029] For preparing a polyether alcohol according to step (2), it ispossible within the present invention to use instead of or besidespropylene oxide all alkoxylating agents, particularly alkylene oxides,which are known to the person skilled in the art, particularly theabove-mentioned compounds.

[0030] In cases where, besides the alkoxylating agent obtained accordingto step (1), particularly propylene oxide, at least one furtheralkoxylating agent, particularly a further alkylene oxide is used, it ispossible within the present invention that a mixture of the alkoxylatingagent as obtained according to step (1), particularly propylene oxide,and at least one further alkoxylating agent, particularly alkyleneoxide, is employed. It is, however, also possible within the presentinvention that the alkoxylating agent as obtained according to step (1),particularly propylene oxide, and the at least one further alkoxylatingagent, particularly an alkylene oxide, are added subsequently.

[0031] The polyether alcohols as obtained according to step (2) may e.g.comprise also block structures. The structure of the polyether alcoholsmay be controlled in wide ranges by appropriate reaction conditions.Suitable reaction conditions for the reaction according to step (2) aree.g. disclosed in WO 99/16775.

[0032] The polyether alcohols as obtained according to step (2) may bemodified for the reaction according to step (3). Regarding thesemodified polyether alcohols, particularly to be mentioned are graftedpolyether polyoles, particularly those which are prepared bypolymerizing styrene and acrylonitril in the presence of polyetheroles;polyurea dispersions (PHD-polyoles) which are prepared by reactingdiisocyanates and diamines in the presence of polyetheroles; andpolyisocyanate polyaddition polyoles (PIPA polyoles), which are preparedby reacting diisocyanates and amino alcohols in the presence ofpolyetheroles.

[0033] The reaction according to step (2) is carried out in the presenceof a catalyst system.

[0034] The catalyst system as used according to the invention in step(2) comprises a metallo-organic pore containing framework material,which in turn comprises a metal ion and an at least bidentate organiccompound, said bidentate organic compound being coordinately bound tothe metal ion. Such catalyst systems are known as such and described ine.g. U.S. Pat. No. 5,648,508, EP-A-0 709 253, J. Sol. State Chem., 152(2000) p. 3-20, Nature 402 (1999), p. 276 seq., Topics in Catalysis 9(1999), p. 105-111, Science 291 (2001), p. 1021-23. An inexpensive wayfor their preparation is the subject of DE 10111230.0. The content ofthe above-mentioned literature, to which reference is made herein, isfully incorporated in the content of the present application.

[0035] The metallo-organic framework materials, as used in the presentinvention, comprise pores, particularly micro- and/or mesopores, whereinmicropores are defined as being pores having a diameter of 2 nm or belowand mesopores being pores having a diameter in the range of above 2 nmto 50 nm, respectively, according to the definition in Pure AppliedChem. 45, p. 71 seq., particularly p. 79 (1976). The presence of themicro- and/or mesopores may be monitored by sorption measurements fordetermining the capacity of the metallo-organic framework materials totake up nitrogen at 77 K according to DIN 66131, 66134. A type-I-form ofthe isothermal curve indicates the presence of micropores. In apreferred embodiment, the specific surface areas, as calculatedaccording to the Langmuir model (DIN 66131, 66134) are preferably above5 M2/g, more preferably above 50 m²/g, particularly above 500 m²/g andmay increase into the region of to above 2000 m²/g.

[0036] As the metal component within the framework material as usedaccording to the present invention, particularly to be mentioned aremetal ions of elements of groups Ia, IIa, IIIa, IVa to VIIIa and Ib toVIb of the periodic system; among those particularly to be mentioned areMg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru,Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Ti, Si,Ge, Sn, Pb, As, Sb, and Bi, more preferably Zn, Cu, Ni, Pd, Pt, Ru, Rhand Co. As metal ions of these elements, particularly to be mentionedare: Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Y³⁺, Ti⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V⁴⁺,^(V2+), Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Mn³⁺, Mn²⁺, Re³⁺, Re²⁺, Fe³⁺,Fe²⁺, Ru³⁺, Ru²⁺,Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺, Rh⁺, Ir²⁺, Ir⁺, Ni²⁺,Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu²⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺,Ga³⁺, In³⁺, Tl³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺,As³⁺, As⁺, Sb⁵⁺, Sb³⁺, Sb⁺and Bi⁵⁺, Bi³⁺, Bi⁺.

[0037] With regard to the preferred metal ions and further detailsregarding the same, we particularly refer to: EP-A 0 790 253,particularly p. 10, 1. 8-30, section “The Metal Ions”, which section isincorporated herein by reference.

[0038] As the at least bidentate organic compound, which is capable tocoordinate with the metal ion, in principle all compounds which aresuitable for this purpose and which fulfill the above requirements ofbeing at least bidentate, may be used. The organic compound must have atleast two centers, which are capable to coordinate with the metal ionsof a metal salt, particularly with the metals of the aforementionedgroups. With regard to the at least bidentate organic compound, specificmention is to be made of compounds having

[0039] i) an alkyl group substructure, having from 1 to 10 carbon atoms,

[0040] ii) an aryl group substructure, having from 1 to 5 phenyl rings,

[0041] iii) an alkyl or aryl amine substructure, consisting of alkylgroups having from 1 to 10 carbon atoms or aryl groups having from 1 to5 phenyl rings,

[0042] said substructures having bound thereto at least one at leastbidentate functional group “X”, which is covalently bound to thesubstructure of said compound, and wherein X is selected from the groupconsisting of

[0043] CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄,Ge(SH)₄, Sn(SH)₃, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, CH(RSH)₂,C(RSH)₃, CH(RNH₂)₂, C(RNH₂)₃, CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C(RCN)₃,wherein R is an alkyl group having from 1 to 5 carbon atoms, or an arylgroup consisting of 1 to 2 phenyl rings, and CH(SH)₂, C(SH)₃, CH(NH₂)₂,C(NH₂)₂, CH(OH)₂, C(OH)₃, CH(CN)₂ and C(CN)₃.

[0044] Particularly to be mentioned are substituted or unsubstituted,mono- or polynuclear aromatic di-, tri- and tetracarboxylic acids andsubstituted or unsubstituted, aromatic, at least one hetero atomcomprising aromatic di-, tri- and tetracarboxylic acids, which have oneor more nuclei.

[0045] A preferred ligand is 1,3,5-benzene tricarboxyllic acid (BCT),particularly preferred metal ions are Co²⁺and Zn²⁺.

[0046] Besides the at least bidentate organic compound, the frameworkmaterial as used in accordance with the present invention may alsocomprise one or more monodentate ligands, which are preferably derivedfrom the following mono-dentate substances:

[0047] a. alkyl amines and their corresponding alkyl ammonium salts,containing linear, branched, or cyclic aliphatic groups, having from 1to 20 carbon atoms (and their corresponding ammonium salts);

[0048] b. aryl amines and their corresponding aryl ammonium salts havingfrom 1 to 5 phenyl rings;

[0049] c. alkyl phosphonium salts, containing linear, branched, orcyclic aliphatic groups, having from 1 to 20 carbon atoms;

[0050] d. aryl phosphonium salts, having from 1 to 5 phenyl rings;

[0051] e. alkyl organic acids and the corresponding alkyl organic anions(and salts) containing linear, branched, or cyclic aliphatic groups,having from 1 to 20 carbon atoms;

[0052] f. aryl organic acids and their corresponding aryl organic anionsand salts, 5 having from 1 to 5 phenyl rings;

[0053] g. aliphatic alcohols, containing linear, branched, or cyclicaliphatic groups, having from 1 to 20 carbon atoms;

[0054] h. aryl alcohols having from 1 to 5 phenyl rings;

[0055] i. inorganic anions from the group consisting of: sulfate,nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate,dihydrogen phosphate, diphosphate, triphosphate, phosphate, phosphite,chloride, chlorate, bromide, bromate, iodide, iodate, carbonate,bicarbonate, and the corresponding acids and salts of the aforementionedinorganic anions,

[0056] j. ammonia, carbon dioxide, methane, oxygen, ethylene, hexane,benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene,thiophene, pyridine, acetone, 1-2-dichloroethane, methylenechloride,tetrahydrofuran, ehtanolamine, triethylamine and trifluoromethylsulfonicacid.

[0057] Further details regarding the at least bidentate organiccompounds and the monodentate substances, from which the ligands of theframework material as used in the present application are derived, maybe deduced from EP-A 0 790 253, whose respective content is incorporatedinto the present application by reference.

[0058] Particularly preferred are within the present applicationframework materials of the kind described herein, which comprise Zn²+asa metal ion and ligands derived from teraphthalic acid as the bidentatecompound, which are known as MOF-5 in the literature.

[0059] Further metal ions and at least bidentate organic compounds andmono-dentate substances, which are respectively useful for thepreparation of the framework materials used in the present invention aswell as processes for their preparation are particularly disclosed inEP-A 0 790 253, U.S. Pat. No. 5,648,508 and DE 10111230.0.

[0060] As solvents, which are particularly useful for the preparation ofMOF-5, in addition to the solvents disclosed in the above-referencedliterature dimethyl formamide, diethyl formamide andN-methylpyrollidone, alone, in combination with each other or incombination with other solvents may be used. Within the preparation ofthe framework materials, particularly within the preparation of MOF-5,the solvents and mother liquors are recycled after crystallization inorder to save costs and materials.

[0061] The separation of the framework materials, particularly of MOF-5,from the mother liquor of the crystallization may be achieved byprocedures known in the art such as solid-liquid separations, such ascentrifugation, extraction, filtration, membrane filtration, cross-flowfiltration, flocculation using flocculation adjuvants (non-ionic,cationic and anionic adjuvants) or by the addition of pH shiftingadditives such as salts, acids or bases, by flotation, spray-drying orspray granulation as well as by evaporation of the mother liquor atelevated temperature and/or in vacuo and concentrating of the solid.

[0062] The separated framework materials, particularly MOF-5 may becompounded, melted, extruded, co-extruded, pressed, spinned, foamed andgranulated according to processes known within the processing ofplastics, respectively.

[0063] In step (2) according to the invention, the alkoxylating agent,particularly propylene oxide from step (1) or a mixture of propyleneoxide of step (1) and at least one further alkylene oxide is reactedwith an organic alkoxylatable compound (organic compound).

[0064] Within the present invention, in principle all organic compounds,which can be alkoxylated, may be used. As particularly suitable organiccompounds, the following are to be mentioned:

[0065] water, organic mono- or dicarboxylic acids, such as acrylic acid,methacrylic acid, succenic acid, adipinic acid, phthalic acid andteraphthalic acid, aliphatic and aromatic, optionally N-mono-, N,N- andN,N′-dialkyl-substituted diamine with 1 to 4 carbon atoms in the alkylgroup, such as optionally mono- or dialkyl-substituted ethylenediamine,diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and1,6-hexamethylenediamine, phenylenediamines, 2,3- ,2,4- and2,6-toluylenediamine and 4,4′-, 2,4′- and 2,2′-diamino-di-phenylmethane,alkanolamines, such as ethanolamine, N-methyl- and N-ethyl-ethanolamine,dialkanolamines, such as diethanolamine, N-methyl- andN-ethyl-diethanolamine, and trialkanolamines, such as triethanolamine,and ammonia and polyvalent alcohols, such as monoethyleneglycol,propandiol-1,2 and-1,3 diethyleneglykol, dipropyleneglycol,butanediol-1,4, hexanediol-1,6, glycerol, trimethylolpropane,pentaerytrit, sorbite and saccharose. As the preferred polyetherpolyalcohols, addition products ethylene oxide and/or propylene oxideand water, monoethyleneglycol, diethyleneglykol, propandiol-1,2,diproplyeneglycol, glycerol, trimethylolpropane, ethylendiamine,triethanolamine, pentaerythrit, sorbite and/or saccharose are used aloneor in admixture with each other.

[0066] The organic compounds may also be used in the form ofalkoxylates, particularly those having a molecular weight M_(w) in therange of 62 to 15,000 g/mol.

[0067] Furthermore, also macromolecules having functional groups withactive hydrogen atoms, such as hydroxyl groups, particularly those whichare mentioned in WO 01/16209 may be used.

[0068] The polyether alcohols as obtained in step (2) may be reactedwith isocyanates in step (3). Step (3) may be carried out directly afterstep (2). It is also possible that an additional step, particularly apurification step, may be carried out between step (2) and (3).

[0069] Within the present invention, one or more isocyanates may beused. Besides the polyether alcohols as obtained according to step (2)within the reaction according to step (3), further components havinggroups which are reactive towards isocyanates, particularly those havinghydroxyl groups, may be additionally used.

[0070] As further OH-components, use can be made of e.g. polyesters,further polyethers, polyacetales, polycarbonates, polyesterethers, andsimilar compounds.

[0071] Suitable polyesterpolyoles may be prepared by reacting organicdicarboxylic acids having 2 to 23 carbon atoms, preferably aliphaticdicarboxylic acids having 4 to 6 carbon atoms, with polyvalent alcohols,preferably dioles, respectively having 2 to 12 carbon atoms, preferably2 to 6 carbon atoms. As the dicarboxylic acids, the following may bepreferably used:

[0072] succinic acid, glutaric acid, adipinic acid, suberic acid,azelaic acid, sebacinic acid, decanedicarboxylic acid, maleic acid,fumaric acid, phthalic acid, isophthalic acid and teraphthalic acid. Thedicarboxylic acids may be used alone or in admixture with each other.Instead of the free dicarboxylic acid, also the correspondingdicarboxylic acid derivatives, such as dicarboxylic esters of alcoholshaving 1 to 4 carbon atoms or dicarboxylic acid anhydrides may be used.Examples for polyvalent alcohols are:

[0073] ethanediole, diethyleneglycol, 1,2- and 1,3-propanediole,dipropyleneglycol, 1,4-butanediole, 1,5-pentanediole, 1,6-hexanediole,1,10-decanediole, 1,12-dodecanediole, glycerol and trimethylolpropane.Preferably used are ethanediole, diethyleneglycol, 1,4-butanediole,1,5-pentanediole, 1,6-hexanediole, glycerol and/or trimethylolpropane.Furthermore, polyesterpolyoles made of lactones, e.g. caprolactone orhydroxy carboxylic acid, such as α-hxydroxycarpronic acid may be used.For the preparation of the polyesterpolyoles, the organic, e.g. aromaticor preferably aliphatic polycarboxylic acids and/or derivatives thereofmay be reacted with the polyvalent alcohol in the absence of a catalystor preferably in the presence of an esterifying catalyst. Preferably,the reaction is carried out in an inert atmosphere, e.g. in a nitrogen,carbon monoxide, helium, argon, etc. atmosphere. The whole reaction iscarried out in a melt at temperatures from 150 to 250° C., preferably180 to 220° C., optionally under reduced pressure, up to the desiredacid number, which preferably is lower than 10, more preferably lowerthan 2. According to a preferred embodiment of this condensationreaction, the mixture to be esterified is first reacted up to an acidnumber of 80 to 30, preferably 40 to 30, under normal pressure and atthe above-mentioned temperatures, and subsequently polycondensated at apressure of lower than 500 mbar, preferably 50 to 150 mbar. Asesterifying catalyst, mention can be made of e.g. Fe, Cd, Co, Pb, Zn,Sb, Mg, Ti and Sn catalysts in the form of metals, metal oxides or metalsalts. However, the polycondensation may be also carried out in theliquid phase in the presence of a thinning and/or entraining agent, suchas benzene, toluene, xylene or chlorobenzene, in order to azeotropicallydistillate the water generated during condensation. For the preparationof the polyesterpolyoles, the organic polycarboxylic acids and/or acidderivatives and the polyvalent alcohols are preferably polycondensatedin molar ratios of 1:1.8, preferably 1:1.05 to 1:1.2. The obtainedpolyesterpolyoles exhibit preferably a functionality of 2 to 4,particularly 2 to 3 and a hydroxyl number of preferably 22 to 100 mgKOH/g. Furthermore, use can be made of compounds which are reactivetowards isocyanates, such as dioles, trioles and/or polyoles havingmolecular weights of 60 to <400, such as aliphatic, cycloaliphaticand/or araliphatic dioles having 2 to 14, preferably 4 to 10 carbonatoms, such as ethyleneglycol, propoanediole-1,3, decanediole-1,10, o-,m-, p-dihydroxycyclohexane, diethyleneglycol, dipropylenglycol andpreferably butanediole-1,4, hexanediole-1,6 andbis-(2-hydroxyethyl)-hydroquinone; triole, such as 1,2,4-,1,3,5-trihydroxy cyclohexane, glycol and trimethylolproprane; and lowmolecular weight polyalkyleneoxides having hydroxyl groups, such asthose obtained by reacting ethylene oxide and/or 1,2-propylene oxidewith the above-mentioned dioles and/or trioles as an H-functionalcompound.

[0074] According to the present invention, the polyether alcohol of step(2) is reacted with at least one isocyanate. In principle, allisocyanates which are known to the person skilled in the art, may beused within the present invention. Particularly, the following are to bementioned:

[0075] aromatic, araliphatic, aliphatic and/or cycloaliphatic organicisocyanates, preferably diisocyanates.

[0076] The following individual compounds are particularly to bementioned:

[0077] alkylenediisocyanates having 4 to 12 carbon atoms in the alkylenegroup, such as 1,12-dodecanediisocyanate,2-ethyl-tetramethylenediisocyanate-1,4,2-methylpentamethylenediisocyanate-1,5, tetramethylenediisocyanate-1,4,lysinesterdiisocyanate (LDI) and/or hexarmethylenediisocyanate-1,6(HDI); cycloaliphatic diisocyanates, such as cyclohexane-1,3- and1,4-diisocyanate and arbitrary mixtures of these isomers, 2,4- and2,6-hexahydrotoluylenediisocyanate and the respective mixtures ofisomers, 4,4′-, 2,2′- and 2,4′-dicyclohexylmethanediisocyanate and therespective mixtures of isomers and/or1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).

[0078] Furthermore, the following isocyanates are exemplary to bementioned: 2,4- and 2,6-toluyliendiisocyanate and the respectivemixtures of isomers, 4,4′-, 2,4′- and 2,2′-diphenylmethanediisocyanateand the respective mixtures of isomers, mixtures of 4,4′- and2,2′-diphenylmethanediisocyanates,polyphenylpolymethylenepolyisocyanates, mixtures of 4,4′-, 2,4′- and2,2′-diphenylmethanediisocyanates andpolyphenylpolymethylene-polyisocyanates (raw-MDI) and mixtures ofraw-MDI and toluylendiisocyanates. Furthermore, mixtures comprising atleast two of the above-mentioned isocyanates may also be used.Furthermore, modified isocyanates having isocyanurate, bouret, ester,urea, allophanate, carbodiimid, uretdione, and/or urethane groups (inthe following also denoted urethane group modified) containing di-and/or polyisocyanates may be used.

[0079] Among those, the following indivial compounds may be mentioned:

[0080] urethane group containing organic polyisocyanates having anNCO-content of 50 to 10 wt.-%, preferably 35 to 15 wt.-%, relative tothe total weight, such as 4,4′-diphenylmethanediisocyanate, 4,4′- and2,4′-diphenylmethanediisocyanate mixtures, raw-MDI or 2,4- and2,6-toluylendiisocyanates, which are respectively modified, e.g. withlow molecular weight dioles, trioles, dialkyleneglycoles,trialkyleneglycoles or polyoxyalkyleneglycoles having molecular weightsof up to 6000, particularly molecular weights of up to 1500, may be usedalone or in admixture with each other. As the di- orpolyoxyalkyleneglycoles, which may in turn also be used alone or inadmixture with each other, the following are to be mentioned:

[0081] diethylene- and dipropyleneglycol, polyoxyethylene-,polyoxypropylene- and polyoxypropylenepolyoxyetheneglycoles, -triolesand/or tetroles. Furthermore, prepolymers comprising NCO-groups, andrespectively having NCO-contents of 25 to 3.5 wt.-%, preferably 21 to 14wt.-%, respectively relative to the total weight, may be also used.These compounds are prepared from the above-described polyester- and/orpreferably polyether polyoles and 4,4′-diphenylmethanediisocyanate,mixtures of 2,4′- and 4,4′-diphenylmethanediisocyanate, 2,4- and/or2,6-toluylenediisocyanate or raw-MDI. Furthermore, use can also be madeof liquid polyisocyanates containing carbodiimide groups, respectivelyhaving NCO-contents of 36.6 to 15, preferably 31 to 21 wt.-%, relativeto the total weight, e.g. on the basis of 4,4′-, 2,4′- and/or2,2′-diphenylmethanedisocyate and/or 2,4- and/or2,6-toluylenediisocyanate. The modified polyisocyanates may be mixedwith each other or together with non-modified organic polyisocyanates,such as e.g. 2,4′-, 4,4′-diphenylmethanediisocyanate, raw-MDI, 2,4- or2,6-toluylenediisocyanate. As modified isocyanates, preferably use ismade of isocyanurate, biuret and/or urethane group modified aliphaticand/or cycloaliphatic diisocyanates, e.g. those which are alreadymentioned, which are provided with biuret and/or cyanurate groupsaccording to known processes, and which comprise at least one,preferably at least two and more preferably at least three freeisocyanate groups, respectively. The trimerization of the isocyanatesfor preparing isocyanates having isocyanurate groups may be carried outat common temperatures in the presence of known catalysts, such asphosphines and/or phosphorine derivatives, amines, alkali metal salts,metal compounds and/or Mannich bases. Furthermore, trimers ofisocyanates containing isocyanurate groups are furthermore commerciallyavailable. Isocyanates having biuret groups may also be preparedaccording to generally known processes, e.g. by reacting theabove-mentioned diisocyanates with water or diamines, wherein as anintermediate product, a urea derivative is formed. Isocyanatescontaining biuret groups are also commercially available.

[0082] The reaction according to step (3) is carried out underconditions known to the person skilled in the art. Suitable reactionconditions are described in e.g. Becker, Braun “Polyurethanes”,Kunststoffhandbuch, Vol. 7, Carl Hanser, Munich, 3^(rd) Ed., 1993, p.139 to 193.

[0083] Optionally, within the reaction according to step (3), further,low molecular weight compounds may be added as additives. Such compoundsmay be chain extenders or stopping agents. Particularly useful for thispurpose are e.g. primary amino compounds having 2 to about 20, e.g. 2 toabout 12 C-atoms. As examples, the following are to be mentioned:ethylamine, n-propylamine, i-propylamine, n-propylamin,sec.-propylamine, tert.-butylamine, 1-aminoisobutane, substituted amineshaving 2 to about 20 C-atoms, such as2-(N,N-dimethylamino)-1-aminoethane, aminomercaptanes, such as1-amino-2-mercaptoethane, diamines, aliphatic aminoalkohols having 2 toabout 20, preferably 2 to about 12 C-atoms, such as methanolamine,1-amino-3,3-dimethylpentane-5-ol, 2-aminohexane-2′,2″-diethanolamine,1-Amino-2,5-dimethylcyclohexane-4-ol, 2-aminopropanol, 2-aminobutanol,3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol,5-aminopentanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol,1-amino-1-cyclopentane-methanol, 2-amino-2-ethyl-1,3-propandiole,aromatic-aliphatic or aromatic or aromaticcycloaliphatic aminoalcoholshaving 6 to about 20 C-atoms, wherein as the aromatic structuresheterocyclic ring systems or preferably isocyclic ring systems such asnaphthalene or particularly benzene derivatives, such as2-aminobenzylalcohol, 3-(hydroxymethyl)anilin,2-amino-3-phenyl-1-propanol, 2-amino-1-phenylethanol, 2-phenylglycinolor 2-amino-1-phenyl-1,3-propandiole and mixtures of two or more of suchcompounds.

[0084] The reaction according to step (3) may optionally be carried outin the present of a catalyst. Compounds which are suitably used ascatalysts may in principle be all compounds which strongly acceleratethe reaction of isocyanates with compounds being reactive towardsisocyanates, wherein preferably a total content of catalyst of from0.001 to 15 wt.-%, particularly 0.05 to 6 wt.-%, relative to the totalweight of compounds being reactive towards isocyanates is used. In thefollowing, possibly used catalysts are exemplarily mentioned:

[0085] Tertiary amines, such as triethylamine, tributylamine,dimethylbenzylamine, dicyclohexylnethylamine, dimethylcyclohexylamine,N,N,N′,N′-tetramethyldiaminodiethylether, bis(dimethylaminopropyl)urea,N-methyl- and N-ethylmorpholine, N-cyclohexylmorpholine,N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetramethylbutanediamine,N,N,N′,N′-tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine,dimethylpiperazine, N-dimethylaminoethylpiperidine,1,8-diazabicyclo(5.4.0)undecen-7,1,2-dimethylimidazol,1-azabicyclo-(2.2.0)octane, 1,4-diazabicyclo(2.2.2)octan (DABCO),alkonolamine compounds, such as triethanolamine, triisopropanolamine,N-methyl-and N-ethyl diethanolamine, dimethylaminoethanol,2-(N,N-dimethylaminoethoxy)ethanol,N,N,N′,N″-tris(dialkylaminoalkyl)hexahydrotriazines, such asN,N,N′,N″-tris(dimethylaminopropyl)-s-hexahydrotriazine, preferablytriethylenediamine, pentamethylenediethylentriamin and/orbis(dimethylamino)ether; metal salts, e.g. inorganic and/or organiccompounds of Fe, Pb, Zn and/or Sn, in common oxideation stages of themetals, respectively, such as Fe(II)-chloride, Zn-chloride, Pb-octoateand preferably Sn-compounds, such as Sn(II)-compounds, particularlySn-dioctoate, Sn-diethylhexlmaleate and/or Sn(IV)-compounds, such asdialkyl-Sn-di(isooctylmercaptoacetate),dialkyl-Sn-di(2-ethylhexylmaleate),dialkyl-Sn-di(2-ethylhexylmercaptoacetate),dialkyl-Sn-di(isooctylmercaptoacetate), dialkyl-Sn-dilaurate,dialkyl-Sn-dimaleate, dialkyl-Sn-di(mercaptoacetate). Furthermore,amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine,tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide,alkali metal hydroxides, such as sodium hydroxide and alkali metalalcoholates, such as sodium methylate and potasium isopropylate andalkali metal salts of long chain fatty acids having 10 to 20 C-atoms andoptionally OH-groups as side groups, may respectively be used ascatalysts. The exemplarily mentioned catalysts may be used alone or inmixtures of at leas two of the mentioned catalysts.

[0086] Optionally, as adjuvants and/or additives common substances maybe used in the process according to the invention. To be mentioned aree.g. surfactants, internal separating agents, fillers, colorants,pigments, flame retardants, protecting agents against hydrolysis,substances having fungi static and/or bacterial static effects,UV-stabilizers and anti oxygens. Pigments and/or colorants may be usedin order to obtain toned or colored shaped particles.

[0087] In general, the use of a solvent or thinning agent is generallynot required for the reaction according to step (3). However, within apreferred embodiment of said reaction, a solvent or a mixture of two ormore solvents is used. Suitable solvents are e.g. carbohydrates,particularly toluene, xylene or cyclohexane, esters, particularlyethylglycolacetate, ethylacetate or butyacetate, amides, particularlydimethylformamide or N-methylpyrrolidone, sulfoxides, particularlydimethylsulfoxide, ethers, particularly diisopropylether ormethyl-tert.-butyl ether or preferably cyclic ethers, particularly THFor dioxane.

[0088] Furthermore, the present invention also relates to apolyurethane, obtainable by an integrated process, comprising at leastthe following steps,

[0089] (2) reacting at least one organic compound with at least onealkoxylating agent via a process as described above, wherein a polyetheralcohol is obtained;

[0090] (3) reacting the polyether alcohol of step (2) with at least oneisocyanate.

[0091] The polyether alcohol, obtainable according to step (2), which isused for preparing the polyurethane, comprises preferably at least onemixed block of ethylene oxide-propylene oxide-units or a terminalpropylene oxide-block or a combination of both.

[0092] Furthermore, the present invention relates to a process forpreparing a polyurethane foam, starting from a polyurethane, as definedwithin the present invention, that process comprising at least thefollowing step,

[0093] (4) foaming the polyurethane as used as a starting material.

[0094] The present invention also encompasses the polyurethane foam assuch, obtainable by foaming a polyurethane, as obtained by the reactionaccording to step (3).

[0095] The polyurethanes according to the present invention arepredominantly characterized by their low content of impurities, such asC6-compounds. This renders the polyurethanes according to the inventionparticularly suitable for the preparation of polyurethane foams,polyurethane cast skins and elastomers.

[0096] Among the polyurethane foams preferably polyurethane foams areprepared, which are used in the automotive and furniture industry, suchas semi-rigid foams, hard and soft integral foams or RIM (reactioninjection moulding)-materials.

[0097] Processes for the preparation of polyurethane foams are describedin Becker, Braun, “Polyurethanes”, Kunststoffhandbuch, vol. 7, CarlHanser, Munich, 3^(rd) edition, 1993, p. 193 to 265.

[0098] In a preferred embodiment, the present invention relates to apolyurethane, which is derived from a polyether alcohol, obtainableaccording to step (2), which comprises at least one mixed block ofethylene oxide-propylene oxide-units.

[0099] The present invention also relates to a polyurethane, derivedfrom a polyether alcohol, obtainable according to step (2), whichcomprises a terminal propylene oxide block.

[0100] The polyurethane according to the present invention, particularlythe above-mentioned polyurethane, may suitably be used for preparingshaped bodies, particularly shaped bodies made of soft slab-stock foamson the basis of polyurethane. Particularly advantageous in this respectis the low amount of impurities, which results in that no disturbingsmells evolve from the shaped body made of the soft foam.

[0101] In addition thereto, the narrower molecular weight distributiondue to the lower amount of mono-functional side compounds leads to animproved processing during foaming.

[0102] Thus, the present invention also relates to a shaped bodycomprising a polyurethane or a polyurethane foam, respectivelyobtainable by the integrated process of the invention.

[0103] Shaped bodies according to the invention are e.g. mattresses,pillows, shaped bodies for the automotive industry and upholsteryfurniture.

[0104] The following shaped bodies according to the invention are to bementioned:

[0105] soft foams, particularly mattresses, shaped bodies for the innersection of cars, such as car seats, sound absorbent shaped bodies, suchas e.g. carpets and/or upholstery materials, sponges, cushions, pillows,seating furniture, office furniture, particularly seats, back-rests,orthopedic products;

[0106] thermoplastic polyurethanes, particularly for the use of cables,hoses, animal marks, supports for rails, films, shoe soles andaccessories, ski tips and rolled bandages;

[0107] cold casted elastomers, particularly for sheathing of lifting andcarrying belts, impact protection elements, industrial edge protectors,toothed belts, screens for abrasive bulk materials, blades, rolls,coatings for rolls, soil protecting sheets against heavy buildingmachines, parts of housings, housings, coatings for deburring drums,pump elements and pump housings, coatings for the outer parts of tubes,coatings for the inner walls of containers, mattresses for cars,cyclones, pulleys for heavy loads, sheave pulleys, guide pulleys, blockpulleys, coatings for conveyer belts, coatings for channels, saidcoatings being resistant against hydrolysis and abrasion, coatings fortruck loading areas, impact protectors, clutch parts, coatings for bojen(buoys), inline-skate rolls, special rolls, high impact pump elements;

[0108] soft integral foams, particularly steering wheels, seals for airfilters, steering knob, foaming of wires, casings for containers,arm-rests, shoe soles made of polyurethane;

[0109] polyurethane coatings, particularly for floor coverings, refiningof materials, such as wood, leather or metal sheets;

[0110] polyurethane skins, particularly for the use as inserts forshaped bodies, such as dashboards, coverings for car doors, truck andcar seats, floorings;

[0111] rigid polyurethane foams, particularly for the use as dampingmaterial or construction material;

[0112] integral foams, particularly for the use as elements in the innerand outer areas of constructions, complex furnitures, elements for carinteriors, skis and snow boards as well as technical functioning parts;

[0113] RIM-foams, particularly for producing prefabricated units for usein the exterior parts in automotive industry, such as extensive facings,fenders and bumpers;

[0114] Thermoformed foams, particularly for preparing ultra-lightcomposite structures for the use in car manufacture, e.g. as an elementfor roof covers;

[0115] semi-rigid foams, particularly for underfoaming of films, skinsor leather or fiber reinforced construction elements.

[0116] The invention is now further described by way of the followingexamples, which are, however, not meant to limit the scope of thepresent application.

EXAMPLES

[0117]FIG. 1 shows a X-ray powder diffractogramm of the MOF-5 catalystas prepared according to Example 1 (the ordinate Y describes Lin inCounts and the abscisse X the 2-Theta-Scale).

[0118]FIG. 2 shows the sorptionisotherme of said catalyst (the ordinateVA describes the volume as absorbed in cm 3/g STP and the abscisse RPthe relative pressure (P/PO)).

EXAMPLE 1 Preparation of MOF-5

[0119] Molar Starting Material Amount Calculated Experimentalterephthalic acid  12.3 mmol  2.04 g  2.04 g Zinc nitrate-tetra-hy- 36.98 mmol  9.67 g  9.68 g drate diethylformamide 2568.8 mmol 282.2 g282.2 g (Merck)

[0120] The above-mentioned amounts of the starting materials weredissolved in a beaker in the order diethylformamide, terephthalic acidand zinc nitride. The resulting solution was introduced into twoautoclaves (250 ml), having respectively inner walls which were coveredby teflon.

[0121] The crystallization occurred at 105° C. within twenty hours.Subsequently, the orange solvent was decanted from the yellow crystals,said crystals were again covered by 20 ml dimethylformamide, the latterbeing again decanted. This procedure was repeated three times.Subsequently, 20 ml chloroform were poured onto the solid, which waswashed and decanted by said solvent two times.

[0122] The crystals (14.4 g), which were still moist, were introducedinto a vacuum device and first at room temperature in vacuo (10⁻⁴ mbar),afterwards dried at 120° C.

[0123] Subsequently, the resulting product was characterized by X-raypowder diffraction and an adsorptive determination of micropores. Theresulting product shows the X-ray diffractogramm according to FIG. 1,which coincides with MOF-5.

[0124] The determination of the sorptionsisotherme, as depicted in FIG.2, with argon (87K; Micromeritics ASAP 2010) shows an isotherme of typeI, being typical for microporous materials, and having a specificsurface area of 3020 m²/g, calculated according to Langmuir, and amicropore volume of 0.97 ml/g (at a relative pressure pp^(o)=0,4).

EXAMPLE 2 Alkoxylation of Dipropylene Glycol with Propylene Oxide

[0125] Dipropylene glycol (33.5 g corresponding to 0.25 mol) and 0.75 gof the catalyst prepared according to Example 1 were introduced in anautoclave. Subsequently, the autoclave was filled with 116 g propyleneoxide (2 mol). The reaction was carried out at 135° C. and a maximumpressure of 12.1 bar, and in total 2.44 mol propylene oxide/mol startingmaterial were reacted to obtain a polyol.

EXAMPLE 3 Alkoxylation of Methyl Dipropylene Glycol with Ethylene Oxide

[0126] Methyl dipropylene glycol (30 g corresponding to 0.25 mol) and0.59 g of the catalyst as prepared according to Example 1 wereintroduced in an autoclave. The autoclave was then filled with 88 gethylene oxide (2 mol). The reaction was carried out at 135° C. and amaximum pressure of 21.2 bar. In total, 2.45 mol ethylene oxide/molstarting compound were reacted to obtain a polyol.

EXAMPLE 4 Alkoxylation of Acrylic Acid with Ethylene Oxide

[0127] 33.2 g acrylic acid (stabilized with 2,2′,6,6′-tetramethyl-4-hydroxypiperidine-N-oxide and phenothiazine) and 0.5g catalyst of Example 1 were weighed into a 300 ml steering autoclaveunder nitrogen atmosphere. The autoclave was closed and pressurized with10 bar nitrogen. Upon steering 20 g ethylene oxide were subsequentlyintroduced via a screw press. After five hours at 50° C. the catalystwas filtered off and the raw product was analyzed by gas chromatography.Based on the area percentages the following composition of the solution(residual ethylene oxide not considered):

[0128] Acrylic acid 76%, monoethylene glycol acrylate 10%, diethyleneglycol acrylate 9%, other side products 5%.

1-12. (Cancelled).
 13. A process for the alkoxylation of organiccompounds, which comprises: reacting at least one organic compound,which is capable of being alkoxylated, with at least one alkoxylationagent in the presence of a catalyst system to form a polyether alcohol,wherein the catalyst system comprises a metallo-organic frameworkmaterial comprising pores and at least one metal ion and at least one atleast bidentate organic compound, which is coordinately bounded to saidmetal ion.
 14. A process according to claim 13, wherein the metal ion isselected among elements of groups Ia, Ia, IIIa, IVa to VIIIa and Ib toVIb of the periodic table of the elements.
 15. A process according toclaim 13, wherein the bidentate organic compound is selected amongsubstituted or unsubstituted aromatic polycarboxylic acids, which maycomprise one or more nuclei; and substituted or unsubstituted aromaticpolycarboxylic acids, which comprise at least one heteroatom and whichmay have one or more nuclei.
 16. A process according to claim 13,wherein the metallo-organic framework material comprising pores exhibitsa specific surface area, as determined via adsorption (BET according toDIN 66131) of larger than 20 m²/g.
 17. A process according to claim 13,wherein the alkoxylation agent is elected among mono- ormulti-functional epoxides having 2 to 30 carbon atoms and mono-ormulti-functional polyetherpolyoles having a molar mass of above 600g/mol and a mixture of two or more thereof.
 18. An integrated processfor the preparation of a polyurethane comprising at least the followingsteps, (2) reacting at least one organic compound, which is capable ofbeing alkoxylated, with at least one alkoxylating agent via a processaccording to claim 13, to form a polyether alcohol; (3) reacting thepolyether alcohol of step (2) with at least one isocyanate.
 19. Aprocess according to claim 18, wherein the alkoxylating agent ispropylene oxide, which has been obtained in a step (1) by reactingpropylene with oxygen, hydrogen and oxygen; hydrogen peroxide; organichydroperoxides; or halohydrins.
 20. A process according to claim 19,wherein the propylene oxide has been obtained by reacting propylene withhydrogen peroxide.
 21. A process according to claim 19, wherein thepropylene oxide has been obtained by reacting propylene with hydrogenperoxide in the presence of a catalyst comprising a zeolitic material.22. A process according to claim 19, wherein the propylene oxide hasbeen obtained by reacting propylene with hydrogen peroxide in thepresence of a catalyst comprising a titanium containing zeoliticmaterial having TS-1 structure.
 23. A polyurethane, obtainable by anintegrated process, comprising at least the following steps, (2)reacting at least one organic compound, which is capable of beingalkoxylated, with at least one alkoxylating agent via a processaccording to claim 13, to form a polyether alcohol; (3) reacting thepolyether alcohol of step (2) with at least one isocyanate.
 24. Apolyurethane according to claim 23, wherein the polyether alcohol, whichis obtainable according to step (2) and which is used as a startingmaterial for the preparation of the polyurethane, comprises at least amixed block of ethylene oxide-propylene oxide-units or a terminalpropylene oxide block or a combination of both.
 25. A process forpreparing a polyurethane foam starting from a polyurethane obtainable bya process that comprises the process according to claim 13, whichcomprises at least the following step, (4) foaming of said polyurethane.26. A process for preparing a polyurethane foam starting from apolyurethane obtainable by an integrated process according to claim 23,which comprises at least the following step, (4) foaming of saidpolyurethane.
 27. A polyurethane foam, obtainable by a process accordingto claim 13, which further comprises: reacting the polyether alcoholwith at least one isocyanate and foaming the polyurethane.
 28. Apolyurethane foam, which is prepared by a process comprising: (2)reacting at least one organic compound, which is capable of beingalkoxylated, with at least one alkoxylating agent via a processaccording to claim 13, to form a polyether alcohol; (3) reacting thepolyether alcohol of step (2) with at least one isocyanate; and (4)foaming the polyurethane, which has been obtained in the reactionaccording to step (3).
 29. A shaped body comprising a polyurethane,which is obtainable by a process according to claim
 13. 30. A shapedbody comprising a polyurethane according to claim
 23. 31. A shaped bodycomprising a polyurethane foam obtainable by the process according toclaim
 25. 32. A shaped body comprising a polyurethane foam obtainable bythe process according to claim
 26. 33. A shaped body comprising apolyurethane foam according to claim
 27. 34. A shaped body comprising apolyurethane foam according to claim 28.